EP2096155B1 - Process for production of sealing agent - Google Patents
Process for production of sealing agent Download PDFInfo
- Publication number
- EP2096155B1 EP2096155B1 EP07831912A EP07831912A EP2096155B1 EP 2096155 B1 EP2096155 B1 EP 2096155B1 EP 07831912 A EP07831912 A EP 07831912A EP 07831912 A EP07831912 A EP 07831912A EP 2096155 B1 EP2096155 B1 EP 2096155B1
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- EP
- European Patent Office
- Prior art keywords
- sealing agent
- latex
- stock solution
- production
- aggregate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000007789 sealing Methods 0.000 title claims description 159
- 238000000034 method Methods 0.000 title claims description 50
- 238000004519 manufacturing process Methods 0.000 title claims description 43
- 239000003795 chemical substances by application Substances 0.000 claims description 161
- 229920000126 latex Polymers 0.000 claims description 108
- 239000004816 latex Substances 0.000 claims description 69
- 239000011550 stock solution Substances 0.000 claims description 52
- 239000002245 particle Substances 0.000 claims description 50
- 239000007798 antifreeze agent Substances 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 31
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 29
- 238000002360 preparation method Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 11
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- 239000000839 emulsion Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 6
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 description 26
- 238000009826 distribution Methods 0.000 description 11
- 238000010586 diagram Methods 0.000 description 10
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 9
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 9
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000004931 aggregating effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 229920006174 synthetic rubber latex Polymers 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 108010053481 Antifreeze Proteins Proteins 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920006173 natural rubber latex Polymers 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- -1 stainless Chemical class 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C73/00—Repairing of articles made from plastics or substances in a plastic state, e.g. of articles shaped or produced by using techniques covered by this subclass or subclass B29D
- B29C73/16—Auto-repairing or self-sealing arrangements or agents
- B29C73/163—Sealing compositions or agents, e.g. combined with propellant agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2030/00—Pneumatic or solid tyres or parts thereof
Definitions
- the present invention relates to a process for production of a sealing agent that is injected inside of a pneumatic tire to seal a puncture hole of a pneumatic tire.
- a sealing pump-up device that, when a pneumatic tire (hereinafter, simply referred to as "tire") is punctured, without changing a tire and a wheel, injects a liquid sealing agent inside thereof, raises inside pressure of the tire up to designated pressure to repair the tire is prevailing.
- the sealing agents that are used in this kind of sealing pump-up device, there are ones that are produced by stirring and mixing a rubber latex, a resin emulsion and an anti-freeze agent made of propylene glycol.
- a process for production of a sealing agent which intends to inhibit the sealing agent from generating the aggregates, a process described in, for example, Japanese Patent Application Laid-Open (JP-A) No. 2003-342551 is known.
- a process for production of a sealing agent which is described in JP-A No. 2003-342551 , includes an anti-freeze agent injecting and stirring step where an anti-freeze agent is injected and stirred in a mixed solution of a rubber latex and a stickiness agent contained in a cylindrical vessel.
- the anti-freeze agent injecting and stirring step with the mixed solution stirring by a rotation of a stirring blade of which tip end rotates at such a relatively high speed as 1.0 to 10.0 m/sec, the anti-freeze agent is injected from a plurality of injection ports to a surface of the mixed solution at such a relatively slow speed as 0.01 to 1.01/min per one injection port.
- JP-A No. 2003-342551 further describes that, after the injection of the anti-freeze agent (ethylene glycol) has come to completion in the anti-freeze agent injecting and stirring step, the stirring is preferably continued over for some (for example, 5 min or more) time.
- the sealing agent stock solution is continued stirring for a definite time after the injection of ethylene glycol has come to completion, fine latex aggregates generated in the sealing agent stock solution during stirring may be forwarded to aggregate and grow; as the result, the latex aggregates may be more readily removed from the sealing agent stock solution by filtering than when the latex aggregates are present remained fine in the sealing agent stock solution.
- the invention intends, by considering above-mentioned facts, to provide a process for production of a sealing agent, which may efficiently remove latex aggregates from a sealing agent stock solution and thereby effectively inhibit the sealing agent from gelling owing to the latex aggregates.
- a process for production of a liquid sealing agent according to claim 1 of the invention is a process for production of a liquid sealing agent that contains at least a rubber latex, a resin emulsion and an anti-freeze agent for sealing a puncture hole of a pneumatic tire, the process comprising: a solution preparation step for preparing a sealing agent stock solution by mixing at least a rubber latex and an anti-freeze agent, an aggregate growing step for growing latex aggregates, in which a plurality of rubber latex particles aggregate by leaving the sealing agent stock solution prepared in the solution preparation step still for a predetermined time wherein the predetermined time is 24 hours or more, and an aggregate removing step for removing the latex aggregates from the sealing agent stock solution by filtering the sealing agent stock solution which has undergone the aggregate growing step.
- a process for production of a liquid sealing agent according to claim 2 of the invention the sealing agent stock solution is left still over for 48 hours or more in the aggregate growing step in the process for production of the liquid sealing agent of claim 1.
- a process for production of a sealing agent according to claim 4-3 of the invention the sealing agent stock solution is left still by holding the sealing agent stock solution without stirring in a solution preparation vessel in the aggregate growing step in the process for production of the liquid sealing agent of any one of claims 1 to 2.
- a process for production of a liquid sealing agent according to claim 4 of the invention includes a step of removing latex aggregates from the sealing agent stock solution with a mesh filter by passing the sealing agent stock solution through a mesh filter finer than 50 mesh, in the aggregate removing step in the process for production of the liquid sealing agent of any one of claims 1 to 4.
- the rubber latex contained in the sealing agent stock solution is at least one selected from the group consisting of an SBR latex, an NR latex, an NBR latex, an MBR latex, a BR latex, a carboxyl-modified NBR latex, and a carboxyl-modified SBR latex, in the process for production of the liquid sealing agent of any one of claims 1 to 4.
- the sealing agent stock solution contains 10 to 55% by mass of an anti-freeze agent, and the anti-freeze agent is at least one selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol, in the process for production of the sealing agent of any one of claims 1 to 5.
- latex aggregates may be efficiently removed from a sealing agent stock solution and thereby the sealing agent is effectively inhibited from gelling owing to the latex aggregates.
- Fig. 1A is a process diagram schematically showing a part of a solution preparation step in a process for production of a sealing agent according to an exemplary embodiment of the invention, and an enlarged diagram schematically showing a state by enlarging a mixed solution produced in the solution preparation step.
- a liquid sealing agent produced by a process for production of a liquid sealing agent according to an exemplary embodiment of the invention includes at least a rubber latex, a resin emulsion and an anti-freeze agent.
- an NR (natural rubber) latex or a synthetic rubber latex is preferably used as the rubber latex contained in the sealing agent 10.
- a synthetic rubber latex one kind substance selected from a group consisting of an SBR latex, an NBR latex, an MBR latex, a BR latex, a carboxyl-modified NBR latex, and a carboxyl-modified SBR latex, or a combination of at least two kinds thereof is preferably used.
- the sealing agent 10 preferably contains an anti-freeze agent to prevent freezing in cold climates.
- an anti-freeze agent one kind substance selected from a group consisting of ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol or a mixture of at least two kinds thereof is preferred.
- a content of such anti-freeze agent is preferably in the range of 10 to 55% by mass. This is because when the content is less than 10% by mass, anti-freeze properties at low temperatures are not sufficiently obtained.
- a glycol amount becomes large relative to a rubber latex amount. Accordingly, aggregated rubber latex particles are present dispersed in glycol at the time of puncture repairing and thereby sufficient seal properties are not obtained in some cases.
- the resin emulsion contained in the sealing agent 10 one kind substance selected from a group consisting of a terpene resin, a rosin resin, a tall oil resin, a phenol resin, a petroleum resin and modified products thereof or a mixture of at least two kinds thereof is preferred.
- water may be contained to dilute, as required, and a dispersing agent, an emulsifying agent, a foam stabilizer or a pH adjusting agent such as ammonia, sodium hydroxide or the like which are commonly used may be added.
- a dispersing agent an emulsifying agent, a foam stabilizer or a pH adjusting agent such as ammonia, sodium hydroxide or the like which are commonly used may be added.
- FIGs. 1A to 1D a process for production of a sealing agent according to the present exemplary embodiment, is schematically shown.
- a process for production of a sealing agent according to the exemplary embodiment includes a solution preparation step shown in Figs. 1A to 1B . In the solution preparation step, in the beginning, as shown in Fig.
- a rubber latex, a resin emulsion, a surfactant, and, as required, a predetermined amount of water for controlling a concentration are charged in a solution preparation vessel 12, a stirring blade 14 held under a water surface inside of the solution preparation vessel 12 is rotated to uniformly mix the rubber latex and resin emulsion by a stirring force of the stirring blade 14, and thereby a mixed solution 16 is prepared.
- an anti-freeze agent (PG) 18 that is an anti-freeze agent is dropped on a liquid surface of the mixed solution 16 to mix a predetermined feed amount of the anti-freeze agent 18 in the mixed solution 16.
- the feed amount of the anti-freeze agent 18 is set so that content thereof in the mixed solution 16 may be 10 to 55% by mass.
- the anti-freeze agent 18 dropped in the mixed solution 16 is homogeneously mixed by a stirring blade 14 in the solution preparation vessel 12.
- a sealing agent stock solution 20 having fundamentally same components as the sealing agent 10 (see Fig. 1E ) as a product is prepared.
- a process for production of a sealing agent includes an aggregate growing step shown in Fig. 1C .
- the sealing agent stock solution 20 prepared in the solution preparation step is held (left standing still) without stirring for a standstill time T over at least 24 hr or more and preferably over 48 hr or more in the solution preparation vessel 12.
- the lower limit of the standstill time T may be appropriately varied in the range of 24 hr or more and 48 hr or less depending on the mesh number of a mesh filter that is used in an aggregate removing step (see, Fig. 1D ) described below and so on.
- the upper limit of the standstill time T is not particularly restricted.
- the upper limit value of the standstill time T is preferably set at 480 hr or less.
- a process for production of a sealing agent includes an aggregate removing step shown in Fig. 1D .
- the sealing agent stock solution 20 undergone the aggregate growing step is transferred from the solution preparation vessel 12 into a stock vessel 28 while filtering the sealing agent stock solution 20 with a filter 22.
- the filter 22 includes an outer vessel 23 and a filter member 26 loaded inside of the outer vessel 23.
- the outer vessel 23 is provided with a receiving port 24 and an exhausting port 25, respectively, opened at an upper end portion and a lower end portion.
- the sealing agent stock solution 20 fed through the receiving port 24 is filtered with the filter member 26 loaded in the vessel, exhausted through the exhausting port 25 into the stock vessel 28 as a sealing agent 10 as a product and stored there.
- a metal mesh filter formed into a wire cloth is used, and a metal mesh filter having the mesh number of 50 mesh (an opening diameter of a network is substantially 300 ⁇ m) to 400 mesh (an opening diameter of a network is substantially 30 ⁇ m) is used.
- the filter member 26 having the mesh number of 100 mesh (an opening diameter of a network is substantially 120 ⁇ m) or 200 mesh (an opening diameter of a network is substantially 70 ⁇ m) is used.
- metals such as stainless, an aluminum alloy and so on, which are high in the corrosion resistance, are preferably used.
- a mesh filter finer in the network than 400 mesh may be used as the filter member 26.
- the sealing tends to occur in a short time; accordingly, an exchange or cleaning period of the filter member 26 loaded in the outer vessel 23 has to be sufficiently shortened.
- a porous filter perforated with many fine openings having an opening diameter substantially same as a network of a mesh filter from 50 mesh to 400 mesh may be used or a laminate filter obtained by laminating a mesh filter and a porous filter may be used.
- the sealing agent 10 stored in the stock vessel 28 is filled in a liquid agent vessel 30 having a capacity corresponding to an amount (for example, 200 to 400 g) of the sealing agent 10 necessary for one time puncture repair, followed by closing an injection port of the liquid agent vessel 30 with an inner lid (not shown in the drawing) and an outer lid 32 to store in the liquid agent vessel 30 in a hermetically sealed state.
- the liquid agent vessel 30 is, with both the inner lid and outer lid are removed at the time of puncture repair of a tire, loaded to a sealing pump-up device (not shown in the drawing).
- the sealing pump-up device pressurizes the sealing agent 10 in the liquid agent vessel 30 with a pump to send the sealing agent 10 under pressure through a joint-hose connected to a tire valve of a tire to the inside of the tire.
- a state F in which the mixed solution 16 is enlarged and observed before the addition of the anti-freeze agent 18 prepared in the solution preparation step is schematically shown.
- the mixed solution 16 is enlarged and observed, many rubber latex particles 34 are floating in a solution L containing water, a surfactant and so on. At that time, the rubber latex particles 34 are floating in a state of dispersed in a solution L by an ionic repulsive force of the surfactant.
- particle diameters of the rubber latex particles 34 in the mixed solution 16 are measured with a particle size distribution analyzer, particle diameters of the rubber latex particles 34 had a substantially normal distribution in the range from substantially 30 to 220 nm with a center value in the proximity of 0.1 ⁇ m (100 nm) as shown in Fig. 2A .
- a state G in which the mixed solution 16 (sealing agent stock solution 20) is enlarged and observed immediately after the anti-freeze agent 18 is homogeneously mixed in the solution preparation step is schematically shown.
- the sealing agent stock solution 20 in the solution preparation step is enlarged and observed, a plurality of the rubber latex particles 34 aggregates and thereby latex aggregates 36 are generated in the solution L.
- the anti-freeze agent 18 added to the mixed solution 16 is a viscous liquid very strong in the compatibility with water, moisture is rapidly absorbed from the surrounding rubber latex particles 34 in contact with the anti-freeze agent 18.
- particle diameters of each of the rubber latex particles 34 and the latex aggregates 36 in the mixed solution 16 are measured with a particle size distribution analyzer, particle diameters of simple body of the rubber latex particles 34 had a substantially normal distribution that is in the range from substantially 30 to 220 nm with a center value in the proximity of 0.1 ⁇ m (100 nm) as shown in Fig. 2B and same as that of the rubber latex particles 34 in the mixed solution 16 before the addition of the anti-freeze agent 18.
- the particle diameter of the latex aggregates 36 generated by aggregating a plurality of rubber latex particles 34 had distribution in the range of 2 to 5 ⁇ m.
- the latex aggregates 36 such as mentioned above are present in the sealing agent 10
- a phenomenon where the latex aggregates 36 form cores to promote gelling of the sealing agent tends to occur.
- the existing ratio of the latex aggregates 36 increases, a time until the sealing agent 10 is gelled tends to be shorter; accordingly, the latex aggregates 36 are necessarily removed as much as possible from the sealing agent 10 in order to make the sealing agent 10 stably durable to long time storage (for example, 10 years or more).
- a state H in which a sealing agent stock solution 20 is enlarged and observed immediately after undergoing the aggregate growth step is schematically shown.
- the sealing agent stock solution 20 which has undergone the aggregate growth step is enlarged and observed, it was found that a plurality of latex aggregates 36 generated in the solution L in the solution preparation step were further aggregated and the particle diameters of rubber latex particles 34 present in the solution L were found to be growing (coarsening).
- particle diameters of each of the rubber latex particles 34 and the latex aggregates 36 in the sealing agent stock solution 20 are measured with a particle size distribution analyzer, particle diameters of simple bodies of the rubber latex particles 34 had a substantially normal distribution that is in the range from substantially 30 to 220 nm with a center value in the proximity of 0.1 ⁇ m (100 nm) as shown in Fig. 2C and same as that of the mixed solution 16 before the addition of the anti-freeze agent 18.
- particle diameters thereof were substantially 10 ⁇ m or more (impossible of accurately measuring the upper limit value).
- a sealing agent stock solution 20 held for 48 hr or more in the solution preparation vessel 12 while stirred with a stirring blade 14 was also measured for particle diameters of the rubber latex particles 34 and latex aggregates 36 by use of a particle size distribution analyzer.
- particle diameters of single bodies of the rubber latex particles 34 were same as the sealing agent stock solution 20 undergone the aggregate growth step according to the exemplary embodiment.
- the latex aggregates 36 were distributed in a wide range from 2 to 10 ⁇ m as a whole with some grown to 10 ⁇ m or more. This is assumed because growth and collapse of the latex aggregates 36 are simultaneously caused under influence of a stirring force.
- a state I in which the sealing agent 10 is enlarged and observed immediately after undergoing the aggregate removing step is schematically shown.
- the sealing agent 10 which has undergone the aggregate removing step is enlarged and observed as shown in Fig. 1D , the latex aggregates are substantially completely removed from the solution L and the rubber latex particles 34 were dispersed and floating in the solution L.
- a state J in which a sealing agent 10 is enlarged and observed that is encapsulated in the liquid agent vessel 30 after undergone the aggregate removing step and left for a definite time (for example, 90 days or more under a high temperature environment) is schematically shown.
- a definite time for example, 90 days or more under a high temperature environment
- Sealing agents (Examples A to F) produced by a process for production of a sealing agent according to the invention, and sealing agents (Comparative Examples G and H) produced by a process for production different in producing conditions from the process for production of a sealing agent according to the invention, were subjected to a measurement of an existing ratio (% by volume) of latex aggregates from 2 to 5 ⁇ m contained in each of the sealing agents and evaluation of the storability of each of the sealing agents, and results thereof are shown below (Table 1).
- the existing ratio of the latex aggregates from 2 to 5 ⁇ m contained in the sealing agent was measured with a particle size analyzer LB-500 (trade name, manufactured by Horiba, Ltd.). Furthermore, a sealing agent was subjected to an accelerated test by leaving the sealing agent under a high temperature environment of 80°C, and, in a column of evaluation of the storability, when the sealing agent was gelled after leaving for 40 days, an evaluation mark of "(1)" was written, when the sealing agent was gelled after leaving for 50 days, an evaluation mark of "(2)” was written, when the sealing agent was gelled after leaving for 60 days, an evaluation mark of "(3)” was written, when the sealing agent was gelled after leaving for 90 days, an evaluation mark of "(4)” was written, and when the sealing agent was not gelled after leaving for 90 days, an evaluation mark of "(5)” was written.
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Sealing Material Composition (AREA)
Description
- The present invention relates to a process for production of a sealing agent that is injected inside of a pneumatic tire to seal a puncture hole of a pneumatic tire.
- In recent years, a sealing pump-up device that, when a pneumatic tire (hereinafter, simply referred to as "tire") is punctured, without changing a tire and a wheel, injects a liquid sealing agent inside thereof, raises inside pressure of the tire up to designated pressure to repair the tire is prevailing. Among the sealing agents that are used in this kind of sealing pump-up device, there are ones that are produced by stirring and mixing a rubber latex, a resin emulsion and an anti-freeze agent made of propylene glycol. In such a process of production of a sealing agent, in general, in the beginning, the rubber latex and a tackiness agent are mixed to prepare a mixed solution, and an anti-freeze agent is injected into a vessel of the mixed solution to produce a sealing agent stock solution. However, since propylene glycol that is used as an anti-freeze agent is a viscous liquid very strong in the compatibility with water, when propylene glycol is injected in the mixed solution, moisture is rapidly absorbed from the neighboring rubber latex in contact with the propylene glycol. Accordingly, a phenomenon in that a concentration of rubber particles in the surrounding latex becomes very high, rubber particles fuse each other to form aggregates, and the sealing agent is partially or entirely solidified (gelled) with the aggregates as a core tends to occur.
- As a process for production of a sealing agent, which intends to inhibit the sealing agent from generating the aggregates, a process described in, for example, Japanese Patent Application Laid-Open (JP-A) No.
2003-342551 JP-A No. 2003-342551 - According to the process for production of the sealing agent, which is described in
JP-A No. 2003-342551 -
JP-A No. 2003-342551 - Herein, according to knowledge of the present inventors, there is a fear in that when the latex aggregates are insufficiently removed from the sealing agent stock solution and the latex aggregates remain at a predetermined amount or more in a sealing agent as a product, a phenomenon where the sealing agent is forwarded to gel with the latex aggregates as a core is generated, the sealing ability due to the sealing agent to a puncture hole is deteriorated with time, and in a longer time span, the entire sealing agent is gelled to be incapable of injecting in a tire.
- However, as the result of an experiment that the present inventors conducted to confirm advantages of a process for production of a sealing agent, which is described in
JP-A No. 2003-342551 - The invention intends, by considering above-mentioned facts, to provide a process for production of a sealing agent, which may efficiently remove latex aggregates from a sealing agent stock solution and thereby effectively inhibit the sealing agent from gelling owing to the latex aggregates.
- A process for production of a liquid sealing agent according to claim 1 of the invention, is a process for production of a liquid sealing agent that contains at least a rubber latex, a resin emulsion and an anti-freeze agent for sealing a puncture hole of a pneumatic tire, the process comprising: a solution preparation step for preparing a sealing agent stock solution by mixing at least a rubber latex and an anti-freeze agent, an aggregate growing step for growing latex aggregates, in which a plurality of rubber latex particles aggregate by leaving the sealing agent stock solution prepared in the solution preparation step still for a predetermined time wherein the predetermined time is 24 hours or more, and an aggregate removing step for removing the latex aggregates from the sealing agent stock solution by filtering the sealing agent stock solution which has undergone the aggregate growing step.
- A process for production of a liquid sealing agent according to
claim 2 of the invention, the sealing agent stock solution is left still over for 48 hours or more in the aggregate growing step in the process for production of the liquid sealing agent of claim 1. - A process for production of a sealing agent according to claim 4-3 of the invention, the sealing agent stock solution is left still by holding the sealing agent stock solution without stirring in a solution preparation vessel in the aggregate growing step in the process for production of the liquid sealing agent of any one of claims 1 to 2.
- A process for production of a liquid sealing agent according to claim 4 of the invention, includes a step of removing latex aggregates from the sealing agent stock solution with a mesh filter by passing the sealing agent stock solution through a mesh filter finer than 50 mesh, in the aggregate removing step in the process for production of the liquid sealing agent of any one of claims 1 to 4.
- A process for production of a sealing agent according to
claim 5 of the invention, the rubber latex contained in the sealing agent stock solution is at least one selected from the group consisting of an SBR latex, an NR latex, an NBR latex, an MBR latex, a BR latex, a carboxyl-modified NBR latex, and a carboxyl-modified SBR latex, in the process for production of the liquid sealing agent of any one of claims 1 to 4. - A process for production of a sealing agent according to claim 6 of the invention, the sealing agent stock solution contains 10 to 55% by mass of an anti-freeze agent, and the anti-freeze agent is at least one selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol, in the process for production of the sealing agent of any one of claims 1 to 5.
- According to above-described processes for production of a sealing agent of the invention, latex aggregates may be efficiently removed from a sealing agent stock solution and thereby the sealing agent is effectively inhibited from gelling owing to the latex aggregates.
-
Fig. 1A is a process diagram schematically showing a part of a solution preparation step in a process for production of a sealing agent according to an exemplary embodiment of the invention, and an enlarged diagram schematically showing a state by enlarging a mixed solution produced in the solution preparation step. -
Fig. 1B is a process diagram schematically showing a part of a solution preparation step in a process for production of a sealing agent according to an exemplary embodiment of the invention, and an enlarged diagram schematically showing a state by enlarging a mixed solution produced in the solution preparation step. -
Fig. 1C is a process diagram schematically showing a part of an aggregate growing step in a process for production of a sealing agent according to an exemplary embodiment of the invention, and an enlarged diagram schematically showing a state by enlarging a sealing agent stock solution produced in the aggregate growing step. -
Fig. 1 D is a process diagram schematically showing an aggregate removing step in a process for production of a sealing agent according to an exemplary embodiment of the invention, and an enlarged diagram schematically showing a state by enlarging a sealing agent produced in the aggregate growing step. -
Fig. 1E is a diagram showing a sealing agent undergone an aggregate removing step in a process for production of a sealing agent according to an exemplary embodiment of the invention, and left for a definite period encapsulated in a liquid agent vessel, and an enlarged diagram schematically showing a state by enlarging a sealing agent. -
Fig. 2A is a graph showing a particle size distribution of rubber latex particles and latex aggregates contained in the mixed solution inFig. 1A . -
Fig. 2B is a graph showing a particle size distribution of rubber latex particles and latex aggregates contained in the sealing agent stock solution inFig. 1B . -
Fig. 2C is a graph showing a particle size distribution of rubber latex particles and latex aggregates contained in the sealing agent stock solution inFig. 1C . - In what follows, a process for production of a liquid sealing agent according to an exemplary embodiment of the invention will be described.
- A liquid sealing agent produced by a process for production of a liquid sealing agent according to an exemplary embodiment of the invention (hereinafter, described as "
sealing agent 10" (seeFig. 1D )), includes at least a rubber latex, a resin emulsion and an anti-freeze agent. - Herein, as the rubber latex contained in the
sealing agent 10, an NR (natural rubber) latex or a synthetic rubber latex is preferably used. As the synthetic rubber latex, one kind substance selected from a group consisting of an SBR latex, an NBR latex, an MBR latex, a BR latex, a carboxyl-modified NBR latex, and a carboxyl-modified SBR latex, or a combination of at least two kinds thereof is preferably used. - Furthermore, the
sealing agent 10 preferably contains an anti-freeze agent to prevent freezing in cold climates. As the anti-freeze agent, one kind substance selected from a group consisting of ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol or a mixture of at least two kinds thereof is preferred. A content of such anti-freeze agent is preferably in the range of 10 to 55% by mass. This is because when the content is less than 10% by mass, anti-freeze properties at low temperatures are not sufficiently obtained. On the other hand, when it exceeds 55% by mass, a glycol amount becomes large relative to a rubber latex amount. Accordingly, aggregated rubber latex particles are present dispersed in glycol at the time of puncture repairing and thereby sufficient seal properties are not obtained in some cases. - As the resin emulsion contained in the
sealing agent 10, one kind substance selected from a group consisting of a terpene resin, a rosin resin, a tall oil resin, a phenol resin, a petroleum resin and modified products thereof or a mixture of at least two kinds thereof is preferred. - In the
sealing agent 10, water may be contained to dilute, as required, and a dispersing agent, an emulsifying agent, a foam stabilizer or a pH adjusting agent such as ammonia, sodium hydroxide or the like which are commonly used may be added. - In
Figs. 1A to 1D , a process for production of a sealing agent according to the present exemplary embodiment, is schematically shown. A process for production of a sealing agent according to the exemplary embodiment, includes a solution preparation step shown inFigs. 1A to 1B . In the solution preparation step, in the beginning, as shown inFig. 1A , among components contained in the sealingagent 10, at least a rubber latex, a resin emulsion, a surfactant, and, as required, a predetermined amount of water for controlling a concentration are charged in asolution preparation vessel 12, astirring blade 14 held under a water surface inside of thesolution preparation vessel 12 is rotated to uniformly mix the rubber latex and resin emulsion by a stirring force of thestirring blade 14, and thereby amixed solution 16 is prepared. - In the next place, as shown in
Fig. 1B , with themixed solution 16 stirring by the stirringblade 14, an anti-freeze agent (PG) 18 that is an anti-freeze agent is dropped on a liquid surface of themixed solution 16 to mix a predetermined feed amount of theanti-freeze agent 18 in themixed solution 16. At this time, the feed amount of theanti-freeze agent 18 is set so that content thereof in themixed solution 16 may be 10 to 55% by mass. - In the solution preparation step, the
anti-freeze agent 18 dropped in themixed solution 16 is homogeneously mixed by astirring blade 14 in thesolution preparation vessel 12. Thereby, a sealingagent stock solution 20 having fundamentally same components as the sealing agent 10 (seeFig. 1E ) as a product is prepared. - A process for production of a sealing agent according to the exemplary embodiment, includes an aggregate growing step shown in
Fig. 1C . In the aggregate growing step, the sealingagent stock solution 20 prepared in the solution preparation step is held (left standing still) without stirring for a standstill time T over at least 24 hr or more and preferably over 48 hr or more in thesolution preparation vessel 12. The lower limit of the standstill time T may be appropriately varied in the range of 24 hr or more and 48 hr or less depending on the mesh number of a mesh filter that is used in an aggregate removing step (see,Fig. 1D ) described below and so on. - Furthermore, the upper limit of the standstill time T is not particularly restricted. However, when a restriction on a process time (tact time) at the production of the sealing
agent 10, and a restriction on a stock amount to stock the produced sealingagent 10 are considered, and when a variation of an amount of moisture during storage is considered because an amount of moisture contained in the sealingagent 10 gradually varies depending on evaporation or moisture absorption corresponding to a storage environment, the upper limit value of the standstill time T is preferably set at 480 hr or less. - A process for production of a sealing agent according to the exemplary embodiment, includes an aggregate removing step shown in
Fig. 1D . In the aggregate removing step, the sealingagent stock solution 20 undergone the aggregate growing step is transferred from thesolution preparation vessel 12 into astock vessel 28 while filtering the sealingagent stock solution 20 with afilter 22. Herein, thefilter 22 includes anouter vessel 23 and afilter member 26 loaded inside of theouter vessel 23. Theouter vessel 23 is provided with a receivingport 24 and anexhausting port 25, respectively, opened at an upper end portion and a lower end portion. The sealingagent stock solution 20 fed through the receivingport 24 is filtered with thefilter member 26 loaded in the vessel, exhausted through theexhausting port 25 into thestock vessel 28 as a sealingagent 10 as a product and stored there. - As the
filter member 26, a metal mesh filter formed into a wire cloth is used, and a metal mesh filter having the mesh number of 50 mesh (an opening diameter of a network is substantially 300 µm) to 400 mesh (an opening diameter of a network is substantially 30 µm) is used. Preferably, thefilter member 26 having the mesh number of 100 mesh (an opening diameter of a network is substantially 120 µm) or 200 mesh (an opening diameter of a network is substantially 70 µm) is used. As a material of the mesh filter, metals such as stainless, an aluminum alloy and so on, which are high in the corrosion resistance, are preferably used. A mesh filter finer in the network than 400 mesh may be used as thefilter member 26. However, the sealing tends to occur in a short time; accordingly, an exchange or cleaning period of thefilter member 26 loaded in theouter vessel 23 has to be sufficiently shortened. - Furthermore, as the
filter member 26, a porous filter perforated with many fine openings having an opening diameter substantially same as a network of a mesh filter from 50 mesh to 400 mesh may be used or a laminate filter obtained by laminating a mesh filter and a porous filter may be used. - As shown in
Fig. 1D , the sealingagent 10 stored in thestock vessel 28 is filled in aliquid agent vessel 30 having a capacity corresponding to an amount (for example, 200 to 400 g) of the sealingagent 10 necessary for one time puncture repair, followed by closing an injection port of theliquid agent vessel 30 with an inner lid (not shown in the drawing) and anouter lid 32 to store in theliquid agent vessel 30 in a hermetically sealed state. Theliquid agent vessel 30 is, with both the inner lid and outer lid are removed at the time of puncture repair of a tire, loaded to a sealing pump-up device (not shown in the drawing). The sealing pump-up device pressurizes the sealingagent 10 in theliquid agent vessel 30 with a pump to send the sealingagent 10 under pressure through a joint-hose connected to a tire valve of a tire to the inside of the tire. - In the next place, the
mixed solution 16, the sealingagent stock solution 20 and the sealingagent 10 prepared in the respective steps of a process for production of a sealing agent according to the exemplary embodiment, will be described. - In
Fig. 1A , a state F in which themixed solution 16 is enlarged and observed before the addition of theanti-freeze agent 18 prepared in the solution preparation step is schematically shown. When themixed solution 16 is enlarged and observed, manyrubber latex particles 34 are floating in a solution L containing water, a surfactant and so on. At that time, therubber latex particles 34 are floating in a state of dispersed in a solution L by an ionic repulsive force of the surfactant. - When particle diameters of the
rubber latex particles 34 in themixed solution 16 are measured with a particle size distribution analyzer, particle diameters of therubber latex particles 34 had a substantially normal distribution in the range from substantially 30 to 220 nm with a center value in the proximity of 0.1 µm (100 nm) as shown inFig. 2A . - In
Fig. 1B , a state G in which the mixed solution 16 (sealing agent stock solution 20) is enlarged and observed immediately after theanti-freeze agent 18 is homogeneously mixed in the solution preparation step is schematically shown. When the sealingagent stock solution 20 in the solution preparation step is enlarged and observed, a plurality of therubber latex particles 34 aggregates and thereby latex aggregates 36 are generated in the solution L. This is assumed that, because theanti-freeze agent 18 added to themixed solution 16 is a viscous liquid very strong in the compatibility with water, moisture is rapidly absorbed from the surroundingrubber latex particles 34 in contact with theanti-freeze agent 18. - When particle diameters of each of the
rubber latex particles 34 and the latex aggregates 36 in themixed solution 16 are measured with a particle size distribution analyzer, particle diameters of simple body of therubber latex particles 34 had a substantially normal distribution that is in the range from substantially 30 to 220 nm with a center value in the proximity of 0.1 µm (100 nm) as shown inFig. 2B and same as that of therubber latex particles 34 in themixed solution 16 before the addition of theanti-freeze agent 18. However, the particle diameter of the latex aggregates 36 generated by aggregating a plurality ofrubber latex particles 34, had distribution in the range of 2 to 5 µm. - In the case when the latex aggregates 36 such as mentioned above are present in the sealing
agent 10, a phenomenon where the latex aggregates 36 form cores to promote gelling of the sealing agent tends to occur. At this time, as the existing ratio of the latex aggregates 36 increases, a time until the sealingagent 10 is gelled tends to be shorter; accordingly, the latex aggregates 36 are necessarily removed as much as possible from the sealingagent 10 in order to make the sealingagent 10 stably durable to long time storage (for example, 10 years or more). - In
Fig. 1C , a state H in which a sealingagent stock solution 20 is enlarged and observed immediately after undergoing the aggregate growth step is schematically shown. When the sealingagent stock solution 20 which has undergone the aggregate growth step is enlarged and observed, it was found that a plurality of latex aggregates 36 generated in the solution L in the solution preparation step were further aggregated and the particle diameters ofrubber latex particles 34 present in the solution L were found to be growing (coarsening). - When particle diameters of each of the
rubber latex particles 34 and the latex aggregates 36 in the sealingagent stock solution 20 are measured with a particle size distribution analyzer, particle diameters of simple bodies of therubber latex particles 34 had a substantially normal distribution that is in the range from substantially 30 to 220 nm with a center value in the proximity of 0.1 µm (100 nm) as shown inFig. 2C and same as that of themixed solution 16 before the addition of theanti-freeze agent 18. However, in the latex aggregates 36 rendered coarser by further aggregating a plurality oflatex particles 36, particle diameters thereof were substantially 10 µm or more (impossible of accurately measuring the upper limit value). - Furthermore, in order to compare with the aggregate growth step according to the exemplary embodiment, a sealing
agent stock solution 20 held for 48 hr or more in thesolution preparation vessel 12 while stirred with astirring blade 14 was also measured for particle diameters of therubber latex particles 34 and latex aggregates 36 by use of a particle size distribution analyzer. As the result, particle diameters of single bodies of therubber latex particles 34 were same as the sealingagent stock solution 20 undergone the aggregate growth step according to the exemplary embodiment. However, the latex aggregates 36 were distributed in a wide range from 2 to 10 µm as a whole with some grown to 10 µm or more. This is assumed because growth and collapse of the latex aggregates 36 are simultaneously caused under influence of a stirring force. - In
Fig. 1D , a state I in which the sealingagent 10 is enlarged and observed immediately after undergoing the aggregate removing step is schematically shown. When the sealingagent 10 which has undergone the aggregate removing step is enlarged and observed as shown inFig. 1D , the latex aggregates are substantially completely removed from the solution L and therubber latex particles 34 were dispersed and floating in the solution L. - In
Fig. 1E , a state J in which asealing agent 10 is enlarged and observed that is encapsulated in theliquid agent vessel 30 after undergone the aggregate removing step and left for a definite time (for example, 90 days or more under a high temperature environment) is schematically shown. When the sealingagent 10 that is encapsulated in theliquid agent vessel 30 and left for a long time is observed by enlarging, it is observed that latex aggregates 36 are neither newly formed nor the gelation is forwarded in the solution L. - As the result of the experiments of the inventors, it was confirmed that, when particle diameters of latex aggregates 36 floating in the sealing
agent 10 remains as 2 to 5 µm, even if the sealingagent 10 is filtered with afilter member 26 such as a mesh filter or the like finer than 400 mesh, latex aggregates are hardly removed from the sealingagent 10. However, when the latex aggregates 36 are coarsened to a particle diameter equal to or more than 10 µm, by filtering the sealingagent 10 with afilter member 26 having 50 mesh, latex aggregates 36 having a particle diameter equal to or more than 10 µm are completely removed from the sealingagent 10. - Sealing agents (Examples A to F) produced by a process for production of a sealing agent according to the invention, and sealing agents (Comparative Examples G and H) produced by a process for production different in producing conditions from the process for production of a sealing agent according to the invention, were subjected to a measurement of an existing ratio (% by volume) of latex aggregates from 2 to 5 µm contained in each of the sealing agents and evaluation of the storability of each of the sealing agents, and results thereof are shown below (Table 1).
- The existing ratio of the latex aggregates from 2 to 5 µm contained in the sealing agent was measured with a particle size analyzer LB-500 (trade name, manufactured by Horiba, Ltd.). Furthermore, a sealing agent was subjected to an accelerated test by leaving the sealing agent under a high temperature environment of 80°C, and, in a column of evaluation of the storability, when the sealing agent was gelled after leaving for 40 days, an evaluation mark of "(1)" was written, when the sealing agent was gelled after leaving for 50 days, an evaluation mark of "(2)" was written, when the sealing agent was gelled after leaving for 60 days, an evaluation mark of "(3)" was written, when the sealing agent was gelled after leaving for 90 days, an evaluation mark of "(4)" was written, and when the sealing agent was not gelled after leaving for 90 days, an evaluation mark of "(5)" was written.
-
[Table 1] Comparative Example G Comparative Example H Example A Example B Example C Example D Example E Example F Composition Latex SBR SBR SBR SBR SBR SBR SBR SBR Resin Emulsion Rosin Rosin Rosin Rosin Rosin Rosin Rosin Rosin Anti-freeze Agent PG PG PG PG PG PG PG PG Standstill Time (hr) 0 0 24 48 96 48 48 48 Filter Member (mesh number) - 50 50 50 50 10 50 200 Evaluation of Storability (1) (2) (3) (4) (4) (3) (4) (5) Latex Aggregates from 2 to 5 µm (% by volume) 5.2 3.0 1.5 0.0 0.0 4.2 0.0 0.0 -
- 10:
- Sealing Agent
- 18:
- Propylene glycol (anti-freeze agent)
- 20:
- Sealing Agent Stock Solution
- 26:
- Filter Member (mesh filter)
- 34:
- Rubber latex Particles
- 36:
- Latex Aggregates
Claims (6)
- A process for production of a liquid sealing agent that contains at least a rubber latex, a resin emulsion and an anti-freeze agent for sealing a puncture hole of a pneumatic tire, the process comprising:a solution preparation step for preparing a sealing agent stock solution by mixing at least a rubber latex and an anti-freeze agent;an aggregate growing step for growing aggregates, in which a plurality of rubber latex particles aggregate to grow latex aggregates, by leaving the sealing agent stock solution prepared in the preparation step still for a predetermined time, wherein the predetermined time is 24 hours or more; andan aggregate removing step for removing the latex aggregates from the sealing agent stock solution by filtering the sealing agent stock solution which has undergone the aggregate growing step.
- The process for production of a liquid sealing agent of claim 1, wherein, in the aggregate growing step, the sealing agent stock solution is left still over for 48 hours or more.
- The process for production of a liquid sealing agent of any one of claims 1 to 2, wherein, in the aggregate growing step, the sealing agent stock solution is left still by holding the sealing agent stock solution without stirring in a solution preparation vessel.
- The process for production of a liquid sealing agent of any one of claims 1 to 3, wherein, in the aggregate removing step, the sealing agent stock solution is passed through a mesh filter finer than 50 mesh to remove latex aggregates from the sealing agent stock solution by the mesh filter.
- The process for production of a liquid sealing agent of any one of claims 1 to 4, wherein the rubber latex contained in the sealing agent stock solution is at least one selected from the group consisting of an SBR latex, an NR latex, an NBR latex, an MBR latex, a BR latex, a carboxyl-modified NBR latex, and a carboxyl-modified SBR latex.
- The process for production of a liquid sealing agent of any one of claims 1 to 5, wherein the sealing agent stock solution contains 10 to 55% by mass of an anti-freeze agent, and the anti-freeze agent is at least one selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2006314027A JP2008127463A (en) | 2006-11-21 | 2006-11-21 | Method for producing sealing agent |
PCT/JP2007/072182 WO2008062711A1 (en) | 2006-11-21 | 2007-11-15 | Process for production of sealing agent |
Publications (3)
Publication Number | Publication Date |
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EP2096155A1 EP2096155A1 (en) | 2009-09-02 |
EP2096155A4 EP2096155A4 (en) | 2012-02-22 |
EP2096155B1 true EP2096155B1 (en) | 2013-03-20 |
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ID=39429646
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP07831912A Active EP2096155B1 (en) | 2006-11-21 | 2007-11-15 | Process for production of sealing agent |
Country Status (5)
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US (1) | US8110618B2 (en) |
EP (1) | EP2096155B1 (en) |
JP (1) | JP2008127463A (en) |
CN (1) | CN101547993B (en) |
WO (1) | WO2008062711A1 (en) |
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US9103499B2 (en) * | 2010-12-03 | 2015-08-11 | GM Global Technology Operations LLC | Gas storage tank comprising a liquid sealant |
RU2474600C2 (en) * | 2011-03-15 | 2013-02-10 | Иван Митрофанович Першин | Liquid sealant for pneumatic tyres of vehicles |
JP2021138848A (en) * | 2020-03-05 | 2021-09-16 | 住友ゴム工業株式会社 | Puncture sealant |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2003193029A (en) * | 2001-12-27 | 2003-07-09 | Sumitomo Rubber Ind Ltd | Method for producing puncture sealing agent for tire |
EP1291159B2 (en) | 2001-09-11 | 2011-12-21 | Sumitomo Rubber Industries, Ltd. | Process for producing a puncture sealing agent for a tire |
JP2003193030A (en) * | 2001-12-27 | 2003-07-09 | Sumitomo Rubber Ind Ltd | Method for producing puncture sealing agent for tire |
JP4188623B2 (en) * | 2002-05-29 | 2008-11-26 | 住友ゴム工業株式会社 | Manufacturing method and manufacturing apparatus for tire puncture sealant |
JP4173326B2 (en) * | 2002-07-08 | 2008-10-29 | 住友ゴム工業株式会社 | Tire puncture sealant |
CN100379834C (en) * | 2002-11-27 | 2008-04-09 | 株式会社普利司通 | Puncture sealing agent |
JP4315777B2 (en) * | 2003-10-17 | 2009-08-19 | 住友ゴム工業株式会社 | Tire puncture sealant |
JP4782473B2 (en) * | 2005-05-25 | 2011-09-28 | 株式会社ブリヂストン | Manufacturing method of sealing agent |
-
2006
- 2006-11-21 JP JP2006314027A patent/JP2008127463A/en active Pending
-
2007
- 2007-11-15 CN CN200780043244.6A patent/CN101547993B/en active Active
- 2007-11-15 EP EP07831912A patent/EP2096155B1/en active Active
- 2007-11-15 US US12/515,479 patent/US8110618B2/en active Active
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US20100032612A1 (en) | 2010-02-11 |
CN101547993A (en) | 2009-09-30 |
EP2096155A1 (en) | 2009-09-02 |
EP2096155A4 (en) | 2012-02-22 |
WO2008062711A1 (en) | 2008-05-29 |
JP2008127463A (en) | 2008-06-05 |
CN101547993B (en) | 2012-12-19 |
US8110618B2 (en) | 2012-02-07 |
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